Process for the catalytic production of olefin-sulphur dioxide compounds of high molecular weight



I Patented Oct. 20, 1942 PROCESS FOR THE CATALYTIC PRODUC- TION F OLEFIN- SULPHUR DIOXIDE COM- POUNDS OF HIGH MOLECULAR WEIGHT Frederick E. Frey, Robert Dewey Snow, and Walter A. Schulze, Bartlesville, 0th.,

Petroleum Company,

Phillips assiznon to Bartlesvllle,

Okla, a corporation of Delaware No Drawing. Original application January 28, 1934, Serial No. 708,520. Renewed June 8, 1934. Divided and this application July 28, 1941, Serial No. 404,439

(Ci. 269-9t) 7 Claims.

This invention relates to the manufacture of compounds of high molecular weight by the reaction of sulphur dioxide with unsaturatedorganic compounds, and comprises processes for catalytically inducing or accelerating such reactions; all as more fully hereinafter set iorth and as claimed.

This application is a division of our co-pendinz application, Serial No. 708,520, filed January 26, 1934, renewed June 8, 1938.

The reaction of sulphur dioxide with conjugated diolefins is well known, and results in two products, one crystalline and one amorphous. The use of anticatalytic compounds, and oi high temperatures, has been claimed to favor the exclusive formation of the crystalline modification (Matthews and Strange, U. S. 1,192,259 (1916); Standinger, Ger. 506,839 (1930); Perkins Can. 329,043 (1933)).

The reaction of sulphur dioxide with monoolefins was first reported by Matthews and Elder (Brit. 11,635, 1914) who formed amorphous products of high molecular weight by reacting some of the simpler olefins with sulphur dioxide in the presence of sunlight or other source of actinic light. More recently, Fitch and Frey (application Ser. No. 599,350, filed March 16, 1932, now U. S. Patent 2,128,932 granted September 9. 1938) have described and claimed the process of inducing and carrying out these reactions in the absence of such source of light, by the use of suitable substances which exert a catalytic effect. Among such substances specifically claimed are oxygen and organic peroxides, salts of silver and monovalent copper, and oxides of nitrogen.

We have found that many other substances will induce and promote the reaction of sulphur ,di-

oxide with olefins in the dark. Among such substances are many belonging to the. following classes.

I Nitrates A. Inorganic (1) Metallic (2) Nitric acid (3) Ammonium nitrate (4) Nitrates of amino com- 1 pounds, such as NH4NO: B. Organic (1) Alkyl, such as CzHsNO:

(2)-Aryl (3) Nitrates of organic amines C; Organometallic, such as pheny mercuric nitrate 11 Nitrites A. Dilute nitrous acid B. Nitriteg of metal and amine com- Mixtures of two or more substances from the above classes may be used, provided, of course, that they do not react with each other.

, Inasmuch as the reaction between sulphur dioxide and the unsaturated compound occurs generally in the liquid phase, the catalytic substance must either be soluble in the mixture of sulphur dioxide and unsaturated compound, or must react with one 01 its constituents to form an intermediate compound which is soluble in the reaction mixture. For example, silver nitrate, lithium nitrate, ammonium nitrate, and dilute alcoholic nitric acid, all of which are somewhat soluble in the reaction mixture, carry the reaction rapidly to completion. On the other hand, barium nitrate, zirconium nitrate, titanium nitrate, strontium nitrate and mercuric nitrate, all oi which are relatively insoluble in the reaction mixture, do not start the reaction at once, but after a period oi. induction extending over several days, the reaction begins, and goes to completion at a moderate rate. The fact that the reaction takes place alter a period of induction would seem to indicate the possibility that there has been some chemical reaction between the insoluble added substance and something in the olefin-sulphur dioxide mixture to form a soluble catalyst.

The solubility of a catalytic substance may of course depend upon the presence of added materials or diluents in the reaction mixture, or

upon the relative proportions of olefin and sulphur dioxide present. Consequently, an accurate. quantitative comparison of the aflectiveness of various catalytic substances is difiicult. However, the datain the following column will indicate the comparative eflectiveness of several compounds when added in the. amount of about 0.5

. Uranyl Acetate.

Beryllium nitrate Mercuric nitrate...

' action mixture by the presence of metals higher to 1.0 per cent by weight to a mixture of equal volumes of liquid sulphur dioxide and butene-Z.

TABLE I Percentage conversion of butene-z to reaction product Catalyst Dilute nitric acid Magnesium perchlorate. Perchloric acid.. Thallium nitrate... Calcium nitrate.... Sodium Nitroprusside.... Phenyl Mercuric Nitrate. Mercurlc Nltrate v Triphenylbismuthlne. TetraethylLead Mercury diethyl Mercury di-n-butyl Zirconium Nitrate Titanium Nitrate. Sodium Nitrite...

Barium Nitrate Strontium Nitrate.

d Nitrate... Cobalt Nitrate.. Isoamyl Nitrite. Sodium Chlorate..

Time

Catalyst i 9 16 21 26 35 da. da. da. da. da. da.

Dilute nitric acid Lithium nitrate Ammonium nitrate Ethyl nitrite Potassium nitrate. Magnesium perchloratc Pcrchloric acid Thallium nitrate. Calcium nitrate. Sodium nitroprussid Phenyl mercuric nitrate.

Titanium nitrate. Sodium nitrite- Cobalt nitrate: Isoamyl nitrite. Sodium chlorate In the absence of any such substance the conversion was never at any time appreciable.

We have also found that the soluble nitrates such as those of lithium or ammonium, or dilute o nitric acid, are equally as efiective as silver ni- Other substances having suitable catalytic properties, and favorable solubility in the reaction mixtures, are nitrolic acids, l-nitrolates, and

psuedonitrols. These more soluble catalytic substances are especially suitable for use in our process when reacting sulphur dioxide with an unsaturated compound in the presence of inert diluents, such as. paraflln hydrocarbons.

The above'named substances may be conveniently added to the mixture to be reacted, in the form of a finely ground solid; or they may be added in solution in alcohol or other inert organic solvent, and dispersed throughout the mixture by shaking or stirring,

The products obtained in our process with the use of these catalytic substances are practically identical with those obtained by reacting the same unsaturated'compound with sulphur dioxide in the presence of sunlight.

Examples of the application of this processare:

I. Equimolecular solutions in absolute ethyl alcohol were prepared as ,follows: Saturated AgNOa, 1.6 g. LlNOa per 100 cc., 1.88 g. NH4NO3 per 100 cc. One-half cc. of one of the solutions was added to a tube, containing approximately g. of a mixture of S02 and butene-2, and the extent of the reaction was observed at various times after warming to room temperature and mixing. The data are given in the following table:

Per cent conversion to reaction product Time, hours atalyst 1% 2 a s a 14' 1s AgNO: 60 .100 LlN0| 10' so 100 NH|N0r II. To a mixture, ofequal volumes of sulphur dioxide and oleflns contained in an autoclaveor other pressure vessel is added from 0.01 percent to 0.1 per cent, ormore. by weight, of one of the substances shown above to exert a catalytic efiect upon the reaction. The catalytic substance is dissolved or dispersed throughout the mixture by thorough stirring or shaking, and the reaction is allowed to take place at temperatures within the range of -25 C. to +40? C.

. 111. To a mixtur 'of equal volumes of allyl alcohol and sulphur dioxide is added 0.5 per cent In a few days, in

by weight or lithium nitrate. the dark, th allyl alcohol is completely converted to a solid','white polymer.

In the following claims the phrase soluble in the reaction mixture, or equivalent language, is to be taken as including substances which are actually soluble in the reaction mixture as well as those which apparently react with the mixture to form soluble compounds having catalytic properties.

Having described our invention, what we claim is: r

1. The process of producing high molecular weight heteropolymrs of oleflns and sulphur dioxide which comprises reacting olefins with sulphur dioxide in the presence of a perchlorate.

2. The process of producing high molecular weight heteropolymers of oleflns and sulphur dioxide, which comprises conducting the reaction in the absence of actinic light in the presence of a perchlorate. 3. In a process in which oleflns are reacted 2,299,822 .6. The process of producing high molecular with sulphur dioxide to form high molecular weight heteropolymeric products, the improvementwhich comprises efiecting the reaction in the absence of actinic light by introducing into the reaction mixture a perchlorate.

4. The process of producing high molecular weight heteropolymers of oleflns and sulphur dioxide, which comprises reacting oleflns with sulweight heteropolymers oi oleflns and sulphur dioxide, which comprises reacting oleflns with sulphur dioxide in the presence of perchloric acid.

'7. The process of producing high molecular weight heteropolymers of oleflns and sulphur dioxide, which comprises conducting the reaction in the absence of actinic'light inthe presence of perchloric acid.

FREDERICK E. FREY. WALTER A. SCHULZE. ROBERT DEWEY SNOW. 

